JPS5896608A - Manufacture of polyolefin - Google Patents

Abstract

PURPOSE:To obtain in high productivity a high-bulk density polyolefin under reduced hydrogen cncentration atmosphere, by the use of a catalyst consisting of an organometallic compound and a solid component comprising a reaction product derived from each specific magnesium and silane compound and a halogen- contg. titanium compound. CONSTITUTION:An olefin is (co)polymerized by the use of a catalyst consisting of (A) a solid component comprising a reaction product derived from (i) a compound of formulaI(R<1> and R<2> are each 1-24C hydrocarbon; X is halogen; 0<= m<=2; 0<=n<=2; 0<m+n<=2) (e.g., diethylmagnesium), (ii) a second compound of formula II (R<3>-R<5> are each 1-24C hydrocarbon, alkoxy, H, etc.; R<6> is 1-24C hydrocarbon; 1<=q<=30) (e.g., monomethyl trimethoxysilane) and (iii) a halogen- contg. titanium compound (e.g., titanium tetrachloride) and (B) an organometallic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyolefins using a novel polymerization catalyst.

Conventionally, in this type of technical field, the
No. 05 discloses a catalyst in which a transition metal compound such as a titanium compound is supported on magnesium halide, and Belgian Patent No. 742,112 discloses a catalyst in which magnesium halide and titanium tetrachloride are co-pulverized. catalyst is known.

However, in the production of polyolefins, it is desirable for the catalyst activity to be as high as possible, and from this point of view, Tokukosho! In the method described in No. 5912105, the polymerization activity is still low, and in the method in Belgian Patent No. 742,112, the polymerization activity is quite low, but improvements are still desired.

First, in German Patent No. 2137872, co-pulverization of magnesium halide, titanium tetrachloride, alumina, etc. substantially reduces the amount of magnesium halide used compared to K, but the amount of magnesium halide used is reduced per solid, which can be considered a measure of productivity. No significant increase in activity was observed, and a catalyst with even higher activity is desired.

Further, in the production of polyolefin, it is desirable that the bulk specific gravity of the polymer produced be as high as possible from the viewpoint of productivity and slurry handling. From this point of view, the method described in Japanese Patent Publication No. 39-12105 has a low bulk specific gravity and unsatisfactory polymerization activity, while the method described in Peruvian Patent No. 742,112 has a high polymerization activity. However, it is desired to improve the drawback that the bulk specific gravity of the produced polymer is low.

The present invention improves the above-mentioned drawbacks, provides a novel polymerization catalyst that can obtain polymers with high polymerization activity and high bulk specific gravity in high yields, and allows continuous polymerization to be carried out extremely easily, as well as a novel polymerization catalyst that can improve the above-mentioned drawbacks. This method provides a method for polymerizing or copolymerizing olefins, which has extremely high polymerization activity, so the monomer partial pressure during polymerization is low, and the bulk specific gravity of the resulting polymer is high, so productivity can be improved.
In addition, the amount of catalyst remaining in the resulting polymer after polymerization is extremely small, so the catalyst removal step can be omitted in the polyolefin production process, simplifying the polymer treatment process and making it possible to produce polyolefins extremely economically as a whole. can.

In the method of the present invention, since the bulk specific gravity of the obtained polymer is large, the amount of polymer produced per unit polymerization reactor is large.

Furthermore, the advantages of the present invention are that although the bulk specific gravity of the produced polymer is high in terms of particle size, there are few coarse particles and fine particles of 50μ or less, so the continuous polymerization reaction is slow and This facilitates the handling of polymer particles such as centrifugation and powder transportation in polymer processing steps.

Another advantage of the present invention is that, as mentioned above, the polyolefin obtained using the catalyst of the present invention has a large specific gravity, and in order to obtain a polymer with a desired melt index, the hydrogen concentration is required compared to the conventional method. Therefore, the total pressure during polymerization can be made relatively small, which has a large effect on economy and productivity.

In addition, when olefin polymerization is carried out using the catalyst of the present invention, an advantage is that the olefin absorption rate decreases little with time, so that polymerization can be carried out for a long time with a small amount of catalyst.

Furthermore, the polymer obtained using the catalyst of the present invention has an extremely narrow molecular weight distribution, and is characterized by very little formation of low polymers, such as a small amount of hexane extraction. Therefore, it is possible to obtain a product of good quality, such as film grade, which has excellent anti-blocking properties.

The catalyst of the present invention provides a novel catalyst system that has many of these features and improves the drawbacks of the prior art described above. It must be said that it is a great thing to be able to achieve this goal.

゛The present invention will be specifically explained below. That is, the present invention provides a method for polymerizing or copolymerizing an olefin using a solid catalyst component and an organometallic compound as a catalyst, in which the solid catalyst component has at least the following five components (1) general formula R-(OR'')nMgX, -m-n (here, Rj, B2 is a swelling hydrogen residue having 1 to 24 carbon atoms, and X represents a rogen atom. m and n are 0≦m≦2.0≦n
≦2.0 (m+n≦2), 3 (2) General formula R+5t-o±, R6 (where R3
, R4 and R54 represent a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen and 9 represent a halogen, and R6 represents a hydrocarbon residue having 1 to 24 carbon atoms. The present invention relates to a method for producing a polyolefin characterized by comprising a substance obtained by reacting a compound represented by (q is 1≦q≦50) and (3) a halogen-containing titanium compound.

R1n1(OR”8MgX2-m used in the present invention)
Examples of the compounds represented by -, include diethylmagnesium, diimpropylmagnesium, di-n-butylmagnesium, dilee-butylmagnesium, methylmagnesium chloride, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, n-propylmagnesium Chloride, n-butylmagnesium chloride, n-butylmagnesium bromide, 5ee-butylmagnesium chloride, phenylmagnesium chloride, decylmagnesium chloride, methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, n-butoxymagnesium chloride, n- Octoxymagnesium chloride, methylmagnesium methoxide, ethylmagnesium methoxide, n-butylmagnesium ethoxide, IHle-butylmagnesium ethoxide, decylmagnesium ethoxide, jetoxymagnesium, diisoproboxymagnesium, di-n-butoxymagnesium, Examples include Zyrow octoxymagnesium, di-t-butoxymagnesium, Zyrow octoxymagnesium, and the like. It can also be used as a complex with trialkylaluminium, such as a complex of di-n-butylmagnesium and triethylaluminum.

3 General formula R'4Si-0÷, R used in the present invention
・Compounds represented by 4 include monomethyltrimethoxysilane/, monomethyltriethoxysilane, monomethyltri-n-butoxysilane, monomethyltri5ee-butoxysilane, monomethyltriisopropoxysilane, monomethyltripentoxysilane, and monomethyltrioctoxy. Silane, monomethyltristearoxysilane, monomethyltriphenoxysilane, dimethyldimethoxy7rane,
Dimethyljethoxysilane, dimethyldiisopropoxysilane, dimethyldiphenoxysilane, trimethylmonomethoxy 7rane, trimethylmonoethoxysilane, trimethylmonoisopropoxysilane, trimethylmonophenoxysilane, monomethyldimethoxymonochlorosilane, monomethyljethoxymonochlorosilane, monomethyl Monoethoxydichlorosilane, monomethyljethoxymonochlorosilane, monomethyljethoxymonobromosilane, monomethyldiphenoxymonochlorosilane, dimethylmonoethoxymonochlorosilane, monoethyl methoxysilane, monoethyltriethoxysilane, monoethyltriisopropoxysilane, monoethyl Triphenoxysilane, diethyldimethoxysilane, diethyljethoxysilane, diethyldiphenoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane,
Triethylmonophenoxysilane, monoethyldimethoxymonochlorosilane, monoethyldiethoxymonochlorosilane, monoethyldiphenoxymonochlorosilane, monoisopropyltrimethoxysilane, mono-n-butyltrimethoxysilane, mono-n-butyltriethoxysilane, mono-Icc- Butyltriethoxysilane, monophenyltriethoxysilane, diphenyljethoxysilane,
diphenylmonoethoxymonochlorosilane, monomethoxytrichlorosilane, monoethoxytrichlorosilane,
Monoinpropoxytrichlorosilane, mono n-butoxytrichlorosilane, monopentoxytrichlorosilane, monooctoxytrichlorosilane, monostearoxytrichlorosilane, monophenoxytrichlorosilane,
Mono p-methylphenokiditrichlorosilane, dimethoxydichlorosilane, jetoxydichlorosilane, diisopropoxydichlorosilane, di-n-butoxydichlorosilane, dioctoxydichlorosilane, trimethoxymonochlorosilane, triethoxymonochlorosilane, triisopropoxymonochlorosilane , tri-n-butoxymonochlorosilane, tri-5ec-butoxymonochlorosilane, tetraethoxysilane, tetraisoproboxysilane and the above compound are condensed, and the repeating unit is represented by +^1-0+, Alternatively, cyclic poly-4 siloxanes can be mentioned.

Examples of the /10-gen-containing titanium compound used in the present invention include titanium halides, alkoxyno-10-genides, and the like. Preferred titanium compounds include tetravalent titanium compounds and pentavalent O titanium compounds.
OR) rX4-r (where R represents an alkyl group, aryl group, or aralkyl group having 1 to 24 carbon atoms, and
0 Gen atom is shown. r is 0≦r<4. ) are preferred, and titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, monoethoxytrichlorotitanium, jetoxydichlorotitanium, triethoxymonochlorotitanium , monoisopropoxytrichlorotitanium, diynepropoxydichlorotitanium, triisopropoxymonochlorotitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium etc. can be mentioned. Trivalent titanium compounds include trihalogens obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium, or organometallic compounds from groups ■ to ■ of the periodic table. Examples include titanium oxide. Also, the general formula Ti (OR), X4-, (where R has 1 to 1 carbon atoms)
24 represents an alkyl group, an aryl group, or an aralkyl group, and X represents a halogen atom. 8 is a trivalent titanium compound obtained by reducing a tetravalent alkoxy titanium halide represented by O(s (4)) with an organometallic compound of the synchronous body 1 to boro group Kinjo.

In the present invention, tetravalent titanium compounds are most preferred.

(1) General formula R"rn(oR")1Mg in the present invention
Compounds expressed in Table 3 by Xz-m-B, (2) General formula R5+5t-o±, IN
There is no particular restriction on the method of reacting the compound represented by (4) and (3) the halogen-containing titanium compound to obtain the solid catalyst component of the present invention. The reaction can be carried out by contacting with K under heating at 400°C, preferably 50 to 500°C for usually 5 minutes to 20 hours, by co-pulverization, or by a suitable combination of these methods. It's okay. Regarding the reaction order of components (1) to (3) (there is no particular restriction, the three components may be reacted at the same time, or the other 15 minutes may be reacted after reacting the two components.

The inert solvent used at this time is not particularly limited, and hydrocarbon compounds and/or derivatives thereof that do not normally inactivate the Ziegler type catalyst can be used.

Specific examples of these include propane, butane, pentane, hexane, heptane, octane, benzene, toluene, xylene, various aliphatic saturated hydrocarbons such as cyclohexane, aromatic hydrocarbons, alicyclic hydrocarbons, and ethanol and diethyl. Examples include ethers, alcohols such as tetrahydrofuran, ethyl acetate, and ethyl benzoate, ethers, and esters.

The equipment used for co-pulverization is not particularly limited, but ball mills, vibration mills, rod mills, impact mills, etc. are usually used, and conditions such as grinding temperature and grinding time can be easily determined by those skilled in the art depending on the grinding method. It is. Generally the grinding temperature is 0℃~200℃, preferably 20℃
~100°C, and the grinding time is 15 to 50 hours, preferably 1 to 30 hours. Of course, these operations should be carried out in an inert gas atmosphere, and moisture should be avoided as much as possible.

In the present invention, a method of reacting components (1) to (3) in a solution or a method of co-pulverizing a substance obtained by reacting components (1) and (2) in a solution with component (3) is particularly preferred.

Furthermore, in the present invention, in addition to the components (1) to (3), the component (4) is selected from organic halogen compounds, halogenating agents, phosphoric acid esters, electron donors, and polycyclic aromatic compounds. It is also preferably employed to use one or more kinds of compounds. The reaction method when using component (4) is also not particularly limited, but component (1) is used in a solution.
Method for reacting ~(4), substance obtained by reacting components (1), (2), and (4) in solution and component (3)
A method of co-pulverizing is preferably used.

The organic halogen compound used at this time is a compound in which a portion of a saturated or unsaturated aliphatic hydrocarbon, aromatic hydrocarbon, etc. is substituted with a halogen, and includes mono-substituted compounds, di-substituted compounds, tri-substituted compounds, etc. Further, the halogen may be any of fluorine, chlorine, bromine and iodine.

Specifically, these organic halogen compounds include methylene chloride, chloroform, carbon tetrachloride, bromochloromethane, dichlorodifluoromethane, 1-bromo-2-chloroethane, chloroethane, 1,2-dibromo-1,1-
Dichloroethane, 1.1-dichloroethane, 1.2-dichloroethane, 1.2-dichloro-1,1,2,2-tetrafluoroethane, hexachloroethane, pentachloroethane, 1.1.1.2-tetrachloroethane, 1 .1.2.2-tetrachloroethane, 1.1.1-
) dichloroethane, 1,1.2-)9chloroethane,
1-chloropropane, 2-chloropropane, 1.2-dichloropropane, 1.3-dichloropropane, 2.2-
Dichloropropane, 1. tl, 2. 5-Hebutachloropropane to Party B, 1.1.2.2. 3-hexachloropropane, octachloropropane, 1,1.2-)dichloropropane, 1-chlorobutane, 2-chlorobutane, 1-
Chloro-2-methylpropane, 2-chloro-2-methylpropane, 1.2-dichlorobutane, 1.3-dichlorobutane, 1.4-dichlorobutane, λ2-dichlorobutane, 1-chloropentane, 1-chloro Hexane, 1-chloroheptane, 1-chlorooctane, 1-chlorononane, 1-chlorotican, vinyl chloride, 1,1-dichloroethylene, 1,2-dichloroethylene, tetrachloroethylene, 3-chloro-1-propene, i,s-di Chloropropane, chloroprene, oleyl chloride, chlorobenzene, chloronaphthalene, hensilk0'))
', [benziritine, chloroethylbenzene, styrene dichloride, a-chlorocumene and the like.

As a halogenating agent, sulfur chloride, PCIs, PCl5
Nonmetal halides such as ゜5iC14, POCIs
, coc 1. , N0C12,5OCh, 5O2Ch
Examples include non-metallic oxyhalides such as.

represents a hydrocarbon residue having 1 to 24 carbon atoms, each of which may be the same or different), specifically triethyl phosphate, tri-n-butyl phosphate, triphenyl phosphate, tribenzyl phosphate, trioctyl phosphate, tricresyl phosphate, tritolyl phosphate, tricylyl phosphate, diphenylxylenyl phosphate, and the like.

As electron donors, alcohol, ether, ketone,
aldehydes, organic acids, organic acid esters, acid nitrides,
Examples include acid amides, amines, nitriles, and the like.

Alcohol, methyl alcohol, ethyl alcohol, n-7' propyl alcohol, isopropyl alcohol, allyl alcohol, n-butyl alcohol, isobutyl alcohol, 5ee-7' methyl alcohol, t
-butyl alcohol, n-amyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, tepyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, benzyl alcohol, naphthyl alcohol, phenol, cresol, etc. with 1 or more carbon atoms There are 18 types of alcohol.

Examples of the ether include ethers having 2 to 20 atoms such as dimethyl ether, diethyl ether, cyphthyl ether, isoamyl ether, anisole, phenethole, diphenyl ether, phenyl allyl ether, and benzofuran.

Examples of the ketone include ketones having 5 to 18 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl phenyl ketone, ethylphenyl ketone, and diphenyl ketone.

Examples of the aldehyde include aldehydes having 2 to 15 carbon atoms, such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, and nathaldehyde.

Examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, caprylic acid, stearic acid, oxalic acid, malonic acid, co/S-phosphoric acid, adipic acid,
Organic acids having 1 to 24 carbon atoms such as methacrylic acid, benzoic acid, toluic acid, anisic acid, oleic acid, linoleic acid, and lylunic acid can be used.

Examples of organic acid esters include methyl formate, methyl acetate, ethyl acetate, propyl acetate, octyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl methacrylate, methyl benzoate, ethyl benzoate, propyl benzoate, and benzoic acid. Octyl, phenyl benzoate, benzyl benzoate, ethyl 0-methoxybenzoate, ethyl p-methoxybenzoate, butyl p-ethoxybenzoate, methyl p-toluate, ethyl p-)ruylate, p-ethylbenzoic acid Examples include organic acid esters having 2 to 30 carbon atoms, such as ethyl, methyl salicylate, phenyl salicylate, methyl naphthoate, ethyl naphthoate, and ethyl anisate.

Examples of the acid halide include acid halides having 2 to 15 carbon atoms, such as acetyl chloride, penzyl chloride, toluyl chloride, and anisyl chloride.

Examples of acid amides include acetic acid amide, benzoic acid amide, and toluic acid amide.

Examples of the amine include amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylenediamine.

Nitriles include acetonitrile, benzonitrile,
Examples include nitriles such as tolnitrile.

Specific examples of polycyclic aromatic compounds include naphthalene, phenanthrene, triphenylene, chrysene, 4-benzophenanthrene, 1,2-benzochrysene, picene,
Anthracene, tetraphene, 1,2,5.4-dibenzanthracene, pentaphene, 44-penzhentaphene, tetracene, 1,2-henzotetracene, hexaphene, hebetafen, diphenyl, fluorene, biphenylene, perylene, coronene, bisanthene, Examples include obalene, pyrene, berinaphthene, and halogen-substituted products and alkyl-substituted products thereof.

In the present invention, the proportion of ingredients (su~(3)) used is as follows:
1) 100? In contrast, component (2) is 11.1 to 500
f, preferably α5 to 200t.

Moreover, it is most preferable to adjust the amount of the titanium compound of component (3) so that the titanium contained in the catalyst component is within the range of α5 to 20% by weight, which results in a well-balanced activity per titanium and solid content. 1 to 10 wt.- to obtain activity.
A range of is particularly desirable.

In addition, when using component (4), the amount used is component (1
) per 1 mole of component (4) is α01 to 5 moles, preferably α05 to 2 moles.

In the present invention, it is also preferable to use the thus obtained solid catalyst component supported on an oxide of a metal of Groups 1 to 2 of the periodic table.

The oxides of groups n to N of the periodic table to be used are oxides of groups n to N of the periodic table.
- Not only oxides of group V metals alone but also double oxides of these metals are suitable, and of course mixtures thereof may also be used. Specific examples of these metal oxides include MgO
,Cab.

ZnO2 Ba1t, Ba20s, S i 0
2, 5nOs, AlzOn, MgO-Al
2O3,5i (h・Ah03, MgO・SiO snow, M
Examples include gO・CaO11A1203, Al2O3 Fist CaO, etc., but especially 5i02, A140
3, S i OPA 1zos, MgO・Al2O3
is preferred.

The method of supporting a solid catalyst component on an oxide of a metal of group ① to ② of the periodic table is not particularly limited, but for example, component (1), component (3), and the necessary components are supported in an ether compound as a solvent in the presence of the metal oxide. If there is, component (4) is added and reacted, and then the liquid phase is removed by washing, drying, etc., and then component (2) is added together with hydrocarbons such as hexane.
A preferred example is a method in which a solid catalyst component is obtained by adding and reacting.

As the organometallic compound used in the present invention, organometallic compounds of Groups 1 to 1 of the periodic table, which are known as part of Ziegler's catalyst, can be used, but organoaluminum compounds and organozinc compounds are particularly preferred. A specific example is the general formula R5A1. R*AIX, RAIX Goose, RI
AIOR%I'LA1 (OR)X and R3A 1
*Xs organoaluminum compound (R is 1 carbon number
~20 alkyl group or aryl group, X represents a halogen atom, R may be the same or different) or the general formula R, Zn (however, R is an alkyl group having 1 to 20 carbon atoms, and the two parties are the same) - but may also be different), triethylaluminum, triisobutylaluminum, triisobutylaluminum, trile-butylaluminum, tritar
t-butylaluminum, trihexylaluminum,
Specific examples include trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, diethylzinc, and mixtures thereof. In addition, these organometallic compounds and co-K, ethyl benzoate, 0- or p
-) Organic carboxylic acid esters such as ethyl tolyate and ethyl p-anisate can also be used in combination. The amount of the organometallic compound to be used is not particularly limited, but it can usually be used in an amount of 1,111 to 1,001,001 times the amount of the titanium compound.

Olefin polymerization using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization, or gas phase polymerization, and it can be particularly preferably used for gas phase polymerization. Polymerization reaction The polymerization reaction is carried out in the same manner as the usual olefin polymerization reaction using a Ziegler type catalyst. In other words, all reactions involve substantially oxygen,
It is carried out in the absence or presence of an inert hydrocarbon in the absence of water or the like. The polymerization conditions for olefin are a temperature of 20 to 120°C, preferably 50 to 100°C.
The pressure is normal pressure to 70Kt/cj, preferably 2 to 60Kt/cj. Molecular weight can be adjusted by polymerization temperature,
Although it can be controlled to some extent by changing polymerization conditions such as the molar ratio of catalysts, it is effectively achieved by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, two or more multi-stage polymerization reactions with different polymerization conditions such as hydrogen production and polymerization temperature can also be carried out without any problems.

The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with Ziegler's catalyst, and α-olefins having carbons a2 to 12 are particularly preferred, such as ethylene, propylene, 1-butene, hexene-1,4-methylpentene. -1, homopolymerization of a-olefins such as octene-1, and ethylene and propylene, ethylene,! :1-7'
Suitable for copolymerization of ten, ethylene and hexene-1, ethylene and 4-methylpentene-1, ethylene and octene-1, propylene and 1-butene, and copolymerization of ethylene and two or more other a-olefins. used for.

Copolymerization with dienes is also preferably carried out for the purpose of modifying polyolefins. Examples of diene compounds used at this time include butadiene, 1,4-hexadiene, ethylidenenorbornene, dicyclopentadiene, and the like.

Examples will be described below, but these are for illustrative purposes to carry out the present invention, and the present invention is not limited thereto.

Example 1 (a) Production of solid catalyst component 20 ml of ethanol was placed in a 500cc fifth flask equipped with a stirrer.
0-, 20t of ethoxymagnesium chloride (Mg/Cl molar ratio = α81) obtained by HCI treatment of magnesium jetoxide, and aluminum triglee-
Butoxide 15f.

was added and reacted for 3 hours under ethanol reflux.

After the reaction was completed, the supernatant liquid was removed and washed with hexane, then 200-hexane and 5yd of titanium tetrachloride were added, and the reaction was carried out for 2 hours under hexane reflux. After the reaction is complete,
The upper M solution was removed, and the obtained solid catalyst component was diluted with hexane for 3
Washed twice. Solid catalyst component 1? It contained 2219 titanium.

Polymerization A stainless steel autoclave was used as a gas phase polymerization apparatus, and a loop was provided with a blower 1 flow rate regulator and a dry cyclone.The papermaking temperature of the autoclave was adjusted by flowing hot water through the jacket.

The above solid catalyst component was placed in an autoclave adjusted to 80°C.
1] at 5 oq/hr, monomethyltriethoxysilane [
L22 mmol/hr and triethylaluminum were fed at a rate of 5 mmol/hr, and the butene-1/ethylene ratio (molar ratio) in the autoclave gas phase was
Further, each gas was supplied to L27 while adjusting hydrogen to a total pressure of 15 cm, and the gas in the system was circulated using a blower to maintain the total pressure at 10 Kf/d-G. Polymerization was carried out. The produced ethylene copolymer had a bulk specific gravity α37, a melt index (MI) 0.9, and a density 0.9205.

Moreover, the catalyst activity was 314.00 C1 copolymer/fTi.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

This copolymer was measured by the method of ASTM-D1238-65T at 190°C at M2.16 Kf, and the melt index was 2.16, and the melt index MI was measured at a load of 10 Kf. R,
The value (F, R, = MI, .7M1116) was 7:4, and the molecular weight distribution was extremely narrow.

In addition, a film of this copolymer was prepared in boiling hexane for 10
After time extraction, the amount of hexane extracted was 1.8 wt.
%, and the amount extracted was extremely small.

Comparative Example 1 Monomethyltriethoxysilane 2.5 in Example 1
Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 except that 2 was not added. The produced ethylene copolymer has a bulk specific gravity α31 and a density α920.
8, the melt index was 1.5.

Also, the catalyst activity is 24111,000 copolymer/7T
It was i.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but it was found that some polymer had adhered to the inner wall and the stirrer.

Further, the F, R, values of this copolymer were a5, and when the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 5.1 wt%.

Example 2 (a) Production of solid catalyst component 20 ml of ethanol in 5 500 cc flasks equipped with a stirrer
01ft1 20f of ethoxymagnesium chloride (Mg/Cl molar ratio = 171) obtained by MCI treatment of magnesium diethoxide and 102 triethyl phosphate were added and reacted for 3 hours under ethanol reflux. After the reaction, remove the supernatant and add 200% hexane.
31g of water was washed. Then, 7200 m of hexane and 5 Wt of titanium tetrachloride were added, and the mixture was reacted for 2 hours under hexane reflux. After the reaction was completed, the supernatant liquid was removed and washed five times with hexane to obtain a solid catalyst component containing 23q of titanium in 1f.

cb> Polymerization Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 except that the above solid catalyst component was fed at a rate of 5019/hr. The produced ethylene copolymer has a bulk specific gravity α34, a density α9203, and a melt index t.
It was 1. In addition, the catalytic activity is 31a000f copolymer/
It had an extremely high activity of f T i.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

In addition, when the F, R, and 1 sections of this coelectric composite were extracted at 15 and the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 1.7 wt, which was extremely small. .

Example 3 (a) Production of solid catalyst component 2 mL of n-hexane was placed in a 500CC triple flask equipped with a stirrer.
20f of n-butylmagnesium chloride and 15f of aluminum triethoxide were added and reacted for 3 hours under hexane reflux. After the reaction was completed, the supernatant was removed and dried up to obtain a white solid substance.

Next, a stainless steel ball with a diameter of h inches is 25
10F of the above solid material and 1.2 t of titanium tetrachloride were placed in a stainless steel pot with an internal volume of 400 liters, and ball milling was carried out at room temperature under a nitrogen atmosphere for 16 hours.

1 ton of solid catalyst component obtained by ball milling flk contains 2
It contained 519 titanium.

(b) Polymerization Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 except that the above solid catalyst component was fed at a rate of 5019/hr. The produced ethylene copolymer had a bulk specific gravity of 0.35, a density (L9210), and a melt index of 1.2.The catalytic activity was extremely high at 251.GoC1 copolymer/fTl.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

In addition, the F, R, value of the copolymer of keratin is 7.3, and when the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 1.3 vt, which was an extremely small amount. Ta.

Example 4 A 2-ton stainless steel autoclave equipped with an induction stirrer was purged with nitrogen, 1,000 ml of hexane was added, and 1 mmol of triethylaluminum and tetraethoxysilane α were added.
05 mmol and solid catalyst component 1 obtained in Example 1
0 Misaki was added and the temperature was raised to 90° C. with stirring. The vapor pressure of hexane is 2 Kf/-.G, but the total pressure of hydrogen is 4.
8 V4/-・G, then ethylene was added until the total pressure reached 10 Kf/cIA-G to start polymerization, and the autoclave pressure was increased tokLr4/-・
Polymerization was carried out for 1 hour while maintaining the temperature at G. After the polymerization was completed, the polymer slurry was transferred to a beaker, hexane was removed under reduced pressure, and the melt index was 1.3, the density was 19628,
White polyethylene 852 with a bulk specific gravity α35 was obtained. Catalytic activity is 74.50Of polyethylene/fT1・hr
@(4H4 pressure, 1,6501 polyethylene/f solid Φh
It was r・CsH&.

Further, the F and R values of the obtained polyethylene were '19, the molecular weight distribution was extremely narrow compared to Comparative Example 2, and the amount of hexane extracted was extremely small at α15vrt.

Comparative Example 2 Polymerization was carried out for 1 hour in the same manner as in Example 4 except that tetraethoxysilane was not added to obtain white polyethylene 81f having a melt index of 1.5, a density of α9651, and a bulk specific gravity of α31. . Catalytic activity is 7
0.80Of polyethylene/fT1-hr-C2H4 pressure, 1.56Of polyethylene/f solid/hr @C
It was 2H4.

The F and R values of the obtained polyethylene were 93, and the hexane extraction amount was 1.2 ft %.

Example 5 The solid catalyst component obtained in Example 1 was fed at a rate of 50 m/hr, and triethylaluminum and monomethyltriethoxysilane were reacted at a composition (molar ratio) of 5:α22 for 2 hours at room temperature. Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 by feeding the obtained product at a rate of 5 mmol/hr in terms of aluminum. The produced ethylene copolymer had a bulk specific gravity α of 35, a density of 0.920 B, and a melt index of 1.1.

The catalyst activity was extremely high, 294.00C1 copolymer/Ti.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer layer at all.

Further, the F, R, and price values of this copolymer were Z3, and when the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was t7wt, which was an extremely small amount.

Procedural amendment January 6, 1980 Director General of the Patent Office Shima 1) Haruki Tono 1. 1# indication 1983 Patent Application No. 193686 2 Title of invention Process for producing polyolefin 3 Amendment t case Relationship with Patent applicant name (444) Column 6 of the detailed description of the invention in the Nippon Oil Co., Ltd. specification, content of amendment (1) r Ba5s J it on page 25, line 9 of the specification
Correct it as "rAddO".

(2) Delete “B, O and J” on page 25, line 9 of the specification.
S outside 0. Correct as JkrSn02J.

Claims (1)

[Claims] In a method for polymerizing or copolymerizing olefins using a solid catalyst component and an organometallic compound as a catalyst, the solid catalyst component comprises at least the following five components (1) of the general formula R1-(OR'')nMgX, - 1n-, (
Here, 11, BR represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a /S logen atom. m and n are 0≦m≦2.
0≦n≦2.0<m+n≦2), 3 represents a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen or a halogen, and has an R mo carbon number of 1 to 24. Indicates a hydrocarbon residue. q is 1≦q≦30); and (3) a substance obtained by reacting a halogen-containing titanium compound.